Phases of NH4 AlF4 and AlF3

ABSTRACT

New crystalline phases of the fluoroaluminum compounds NH 4  AlF 4  and AlF 3  and processes for their preparation are disclosed.

The present invention relates to new phases of the fluoroaluminum compounds NH₄ AlF₄ and AlF₃, processes for their preparation, and a process for the preparation of known crystalline phases of AlF₃ from the new one.

The compound alpha-NH₄ AlF₄ is well known and has been prepared via a route involving direct combination of aqueous NH₄ F and AlF₃, or by thermal decomposition of (NH₄)₃ (AlF₆). It has an extended fluoro bridged network layer structure in the solid state characterized by a square network of corner linked AlF₆ octahedra with ammonium ions between the layers. See Knop et al., Can. J. Chem. 1985, 63, 516. Thermal decomposition of alpha-NH₄ AlF₄ to alpha and beta phases of AlF₃ has also been reported in Shinn et al., Inorg. Chem. 1966, 5, 1927-1933.

Fluoroaluminum compounds, particularly AlF₃, are important solid-state catalysts for chlorofluorocarbon isomerization and fluorination. AlF₃ is known to exist in several crystalline phases referred to as "alpha", "beta", "gamma" and the like. Existing art for preparing fluoroaluminum catalysts includes pyrolysis of precursors obtained from aqueous solution (usually with added HF), treatment of Al₂ O₃ with HF at elevated temperature, and treatment of AlCl₃ with HF or chlorofluorocarbons. From aqueous solution, compounds such as M⁺ AlF₄ (H₂ O)₂ -, (M⁺)₂ AlF₅ (H₂ O)⁻², or (M⁺)₃ AlF₆ ⁻³, have been obtained. When pyrolyzed the aquo compounds lose primarily water, and if the cation M⁺ is capable of decomposition or has a volatile fluoro compound, HF or MF is also lost. However, traces of oxygen tend to remain behind giving rise to small amounts of hydroxy- or oxy-aluminum species.

It has been established that the crystal phase of fluoroaluminum compounds is important to their catalytic properties. Thus it is desirable to control the crystal phase and the amount of hydroxy- or oxy-aluminum species in order to control use as catalyst. The present invention provides a new crystal phase of AlF₃, and a new crystal phase of NH₄ AlF₄, a precursor to AlF₃, and methods for their preparation.

SUMMARY OF THE INVENTION

The present invention comprises a beta phase of NH₄ AlF₄. This phase has a space group I4/mcm with unit cell parameters a of 11.64Å (1.164 nm) and c of 12.66Å (1.266 nm) at 25° C. The present invention further comprises a kappa phase of AlF₃ having space group P4/mbm, and unit cell parameters a of 11.41Å (1.141 nm) and c of 3.54Å (354 nm).

The present invention further comprises a process for the preparation of the beta phase of NH₄ AlF₄ comprising heating pyridineHAlF₄ with formamide. The present invention further comprises a process for the preparation of the kappa phase of AlF₃ comprising the pyrolysis of beta-NH₄ AlF₄.

The present invention further comprises a process for the preparation of the alpha phase of AlF₃ comprising the pyrolysis of the kappa phase of AlF₃.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts the powder X-ray diffraction pattern of the beta phase of NH₄ AlF₄.

FIG. 2A depicts the crystalline structure of one layer of the beta phase of NH₄ AlF₄. FIG. 2B depicts a side view of the crystalline structure of the beta phase of NH₄ AlF₄.

FIG. 3 depicts the powder X-ray diffraction pattern of the kappa phase of AlF₃.

FIG. 4A depicts the crystalline structure of two layers of the kappa phase of AlF₃. FIG. 4B depicts a side view of the crystalline structure of the kappa phase of AlF₃.

DETAILED DESCRIPTION OF THE INVENTION

Scheme 1 lists the chemical reactions as equations 1 to 3 for the processes of the present invention and for the preparation of the compounds of the present invention. ##STR1##

The present invention provides a process for the preparation of NH₄ AlF₄ and its isolation as a solid in accordance with the reaction sequence depicted in equation 1. PyridineHAlF₄ is heated under an inert gas, preferably nitrogen, to about 180° C. in formamide solvent. Pyridine is evolved from the solution and nascent HAlF₄ material remains behind. The HAlF₄ reacts with the formamide solvent eliminating carbon monoxide gas. A material having the composition beta-NH₄ AlF₄ is precipitated from solution and isolated using known techniques.

The present invention further comprises a new crystalline phase of NH₄ AlF₄ denoted as the beta (β) phase. This phase has a space group I4/mcm with unit cell parameters a of 11.64Å (1.164 nm) and c of 12.66Å (1.266 nm) at 25° C. Additional details of atomic parameters are provided in Table II of Example 1. The powder X-ray diffraction for beta-NH₄ AlF₄ is depicted in FIG. 1. Major diffraction peaks occur at 13.98, 24.75, 28.08, 28.53, 42.66, 49.88, 50.64 and 57.95 degrees (2θ) using X radiation of 1.54Å (0.154 nm) (CuKα). A "ball anid stick" and a polyhedral representation of its crystalline structure is shown in FIGS. 2A and 2B respectively. The general structure of the beta phase is that of a layered structure wherein each layer is comprised of corner-shared octahedra of AlF₆ units. Four equatorial fluoride ions of each octahedron are shared within the layer while the remaining two axial fluoride ions are terminal and non-bridging and project into the space between the AlF layers. This interlayer space is occupied by the tetrahedral ammonium counterions. Each Al-F layer is constructed of linked AlF₆ octahedra such that rings of 3, 4 and 5 bridged Al atoms are produced. Registry between the layers is not maintained such that the 3,4 and 5 membered rings do not line up and so no channels persist through the structure. This structure closely resembles that of a phase of the material RbAlF₄. The beta phase of NH₄ AlF₄ is useful as a precursor in the preparation of the kappa phase of AlF₃.

The present invention further comprises a process for the preparation of the kappa phase of AlF₃. This process comprises the pyrolysis of beta-NH₄ AlF₄ to generate kappa AlF₃ is summarized in equation 2. Such pyrolysis is conducted in an appropriate furnace or thermogravimetric analyzer at a temperature range of from about 350° C. to about 600° C. preferably at about 550° C. The pyrolysis is preferably conducted in a dry inert atmosphere such as nitrogen, argon, or helium. A typical reaction time is from about 5 minutes to about 8 hours but can be as long as desired. Preferred is about 30 minutes. The reaction is conducted at vacuum to about 100 atm (1×10⁷ Pascals), preferably at from about 0.1 to about 2 atm (1×10⁴ to 2×10⁵ Pascals). The reaction works best if conducted in a flow environment for removal of volatiles. The desired kappa AlF₃ is collected as a solid product.

The present invention further comprises a new crystalline phase of AlF₃ denoted the kappa (κ) phase. This compound has am X-ray diffraction pattern with peaks at 15.48, 17.30, 22.00, 24.62, 25.09, 28.13, 32.28 and 57.02 degrees (2Θ) using X radiation of 1.54Å (0.154 nm) (CuKα) as shown in FIG. 3. The structure of this new phase kappa-AlF₃ has been elucidated by combined X-ray diffraction and neutron powder diffraction analysis and is shown in FIGS. 4A and 4B. The structure revealed by these techniques is previously unknown for AlF₃. This structure is that of corner-shared [AlF₆ ] octahedra which are linked together in a manner reminiscent of the precursor beta-NH₄ AlF₄ structure. The structure can be considered to be constructed of layers of corner shared AlF₆ octahedra in exactly the same connectivity as the layers of the beta-NH₄ AlF₄ precursor (i.e., rings of 3, 4 and 5 F bridged Al atoms). These layers are now in perfect registry--i.e., the various ring sizes line up from layer to layer--producing channels through the structure. The layers are then fused together by Al-F-Al linkages such that all F atoms act as bridges between octahedra and producing a new dense AlF₃ structure.

The kappa-AlF₃ phase has a space group P4/mbm and a unit cell with cell constants a=11.41Å (1.141 nm) and c=3.54Å (0.354 nm) at 25° C. Additional details of atomic parameters are provided in Table IV of Example 2. The kappa phase of AlF₃ is useful as a catalyst in fluorocarbon transformations such as isomerization and fluorination reactions.

The present invention further comprises the preparation of the alpha phase of AlF₃ comprising the calcination or pyrolysis of the kappa phase of AlF₃ as shown in Equation 3. The calcination is conducted at a temperature of from about 600° C. to about 900° C., preferably at about 650° C. Use of a dry inert atmosphere such as nitrogen, argon, or helium is preferred, with the exclusion of water. The reaction can be run for about 30 minutes to about 8 hours, and typically is conducted for about 60 minutes to about 2 hours. A pressure of from vacuum to about 10 atm (1×10⁶ Pascals) can be employed, preferably from about 0.1 to about 2 atm (1×10⁴ to 2×10⁵ Pascals). The desired product is collected as a solid using conventional isolation techniques.

While the alpha phase of AlF₃ is the thermodynamically most stable, the beta, eta, theta and kappa phases do not interconvert amongst themselves. There is, therefore, no structural progression through these phases en route to alpha. The phase of AlF₃ produced in any given synthesis is apparently dictated by the temperature of synthesis and especially by the precursor from which it is made.

EXAMPLE 1 Preparation of beta-NH₄ AlF₄

Inside a nitrogen filled glove box, 5 g of pyHAlF₄ was dissolved in 10 mL of warm formamide solvent. With vigorous stirring, the clear solution was heated to about 180° C. in an open vessel whereupon it began to boil and fizz vigorously. After holding at this temperature for 5 minutes the clear solution began to boil much less vigorously and a translucent pale precipitate appeared. The solution was allowed to cool back to room temperature whereupon the white precipitate (˜2 g) was collected by filtration. The collected solid was washed with methanol and suction dried to a fine white microcrystalline powder. X-ray diffraction powder data is depicted in FIG. 1 and Table I. A sample of this powder was subjected to Rietveld powder diffraction analysis and the structure solved. The data is tabulated below in Table II and the structure is depicted in FIGS. 2A and 2B. The sample was also subjected to chemical analysis: Calcd. for H₄ NAlF₄ : H 3.33%; N 11.57%; F 62.8%; Al 22.3%; Found: H 3.21%; N 11.57%; F 62.2%; Al 22.7%.

                  TABLE I                                                          ______________________________________                                         Beta-NH.sub.4 AlF.sub.4                                                        X-radiation (CuKα) wavelength = 1.54 Å (0.154 nm)                    Peak Angle (2θ).                                                                        D spacing (ang)                                                                            I/Imax, %                                           ______________________________________                                         13.98          6.3361      100                                                 24.75          3.3970      20                                                  28.08          3.1781      46                                                  28.53          3.1287      32                                                  42.66          2.1195      25                                                  49.88          1.8283      19                                                  50.64          1.8026      15                                                  57.95          1.5915      15                                                  ______________________________________                                    

                  TABLE II                                                         ______________________________________                                         Beta-NH.sub.4 AlF.sub.4                                                        Crystal System: tetragonal                                                     Space Group: I4/mcm                                                            Lattice Dimensions:                                                            a: 11.639 Å (1.1639 nm)                                                    c: 12.600 Å (1.2660 nm)                                                    ATOMIC COORDINATES:                                                            SER      NAME         X       Y       Z                                        ______________________________________                                         1        AL(1)        0.50000 0.00000 0.00000                                  2        AL(2)        0.20774 0.07361 0.00000                                  3        F(3)         0.34121 0.00051 0.00000                                  4        F(4)         0.50000 0.00000 0.13580                                  5        F(5)         0.14123 -0.06684                                                                               0.00000                                  6        F(6)         0.28417 0.21583 0.00000                                  7        F(7)         0.20567 0.07783 0.13964                                  8        N(8)*        0.33852 -0.16148                                                                               0.19972                                  9        N(9)*        0.00000 0.00000 0.25000                                  ______________________________________                                          *The fractional occupancy of the N atoms was higher than one, and the          thermal parameters were quite high to compensate for the contributions of      the four hydrogen atoms attached to each nitrogen. The numbers quoted her      were refined from synchrotron data but very similar results were obtained      from the refinement of Scintag data.                                     

EXAMPLE 2

Preparation of kappa-AlF₃

2 g of the beta-NH₄ AlF₄ material prepared as described above in Example 1 was loaded into a quartz boat and loaded into a horizontal tube furnace with quartz liner. Dry nitrogen or dry air was flowed through the liner and across the solid sample at 500 mL/min. The sample was then ramped up in temperature at 10° C./min to 550° C. and held there for 30 minutes. After cooling back to room temperature the white solid was recovered and sent for X-ray diffraction analysis. The resultant powder diffraction pattern is depicted in FIG. 3 and Table III. Detailed Reitveld analysis of such a pattern has been completed and the crystal structure of the new kappa phase AlF₃ determined. Details are listed below in Table IV and the structure is depicted in FIGS. 4A and 4B.

                  TABLE III                                                        ______________________________________                                         Kappa-AlF.sub.3                                                                X-radiation (CuKα) wavelength = 1.54 Å (0.154 nm)                    Peak Angle (2θ)                                                                         D spacing (ang)                                                                            I/Imax, %                                           ______________________________________                                         15.48          5.7243      14                                                  17.30          5.1267      100                                                 22.00          4.0404      24                                                  24.62          3.6157      99                                                  25.09          3.5490      71                                                  28.13          3.1723      44                                                  32.28          2.7731      11                                                  57.02          1.6151      13                                                  ______________________________________                                    

                  TABLE IV                                                         ______________________________________                                         Kappa-AlF.sub.3                                                                Crystal System: tetragonal                                                     Space Group: P4/mbm                                                            Lattice Dimensions:                                                            a: 11.406 Å (1.1406 nm)                                                    c: 3.544 Å (.3554 nm)                                                      ATOMIC COORDINATES AS PRESENTLY REFINED:                                       SER     NAME     X          Y       Z                                          ______________________________________                                         1       AL(1)    0.42426    0.28999 0.00000                                    2       AL(2)    0.50000    0.00000 0.00000                                    4       F(4)     0.42193    0.29602 0.50000                                    5       F(5)     0.35735    0.43218 0.00000                                    6       F(6)     0.50578    0.15368 0.00000                                    8       F(8)     0.28333    0.21667 0.00000                                    10      F(10)    0.50000    0.00000 0.50000                                    ______________________________________                                     

What is claimed is:
 1. A compound comprising the beta phase of NH₄ AlF₄ having space group I4/mcm and having unit cell parameters of a equal to 11.64Å (1.164 mm) and c equal to 12.66Å (1.266 nm) at 25° C.
 2. A compound comprising the kappa phase of AlF₃ having space group P4/mbm and unit cell parameters of a equal to 11.41Å (1.141 nm) and c equal to 3.54Å (0.354 nm).
 3. A process for the preparation of the beta phase of NH₄ AlF₄ comprising reacting pyridineHAlF₄ and formamide solvent.
 4. The process of claim 3 conducted at a temperature of at least about 180° C.
 5. A process for the preparation of the kappa phase of AlF₃ comprising the pyrolysis of beta-NH₄ AlF₄.
 6. The process of claim 5 conducted at a temperature of at least about 350° C.
 7. A process for the preparation of the alpha phase of AlF₃ comprising the pyrolysis of the kappa phase of AlF₃.
 8. The process of claim 7 conducted at a temperature of at least about 650° C.
 9. The process of claim 6 or 8 conducted in a dry inert atmosphere. 